Monomers, Oligomers and Polymers Comprising Thiophene and Selenophene

Abstract

The invention relates to novel mono-, oligo- and polymeric compounds comprising thiophene and selenophene, to their use as semiconductors or charge transport materials, in optical, electro-optical or electronic devices, and to optical, electro-optical or electronic devices comprising the novel compounds.

1 - 21 . (canceled) 
   
   
       22 . A monomeric, oligomeric, or polymeric compound comprising one or more selenophene-2,5-diyl groups and one or more thiophene 2,5-diyl groups, wherein said selenophene-2,5-diyl groups and thiophene 2,5-diyl groups are optionally substituted in the 3- and/or 4-position, with the proviso that said compound does not comprise homopolymers of 2,5-bis(3-octyl-thiophen-2-yl)selenophene. 
   
   
       23 . The monomeric, oligomeric, or polymeric compound of  claim 22 , wherein said compound comprises units of formula I 
     
       
         
         
             
             
         
       
     
     wherein
 R 1 , R 2 , R 3 , R 4 , R 5 , and R 6  
 are, independently of each other, and, in case of multiple occurrence, independently of one another, H; halogen; optionally substituted aryl or heteroaryl; P-Sp-; P*-Sp-; or straight chain, branched, or cyclic alkyl having up to 20 C atoms, optionally mono- or polysubstituted by F, Cl, Br, I, or CN; wherein one or more non-adjacent CH 2  groups are optionally replaced, in each case independently from one another, by —O—, —S—, —NH—, —NR 0 —, —SiR 0 R 00 —, —CO—, —COO—, —OCO—, —O—CO—O—, —S—CO—, —CO—S—, —CX 1 ═CX 2 —, or —C≡C—, with the proviso that O and/or S atoms are not linked directly to one another; 
 
 R 0  and R 00  
 are, independently of each other, H, aryl, or alkyl having up to 12 C atoms; 
 
 X 1  and X 2  
 are, independently of each other, X, F, Cl, or CN; 
 
 P is a polymerisable group; 
 P* is a group that can be converted to or substituted by a polymerisable group P; 
 Sp is a spacer group or a single bond; 
 a, b, c, and d
 are, independently of each other, 0, 1, 2, or 3, wherein the sum of a and c is greater than 1 and the sum of b and d is greater than 1; 
 
 n is an integer greater than or equal to 1; and 
 wherein said recurring units of formula I are identical or different; 
 with the proviso that said compound does not comprise recurring units of formula I wherein a, b, and c are equal to 1; d is equal to 0; R 1  and R 2  are n-C 8 H 17 ; R 3 , R 4 , R 5 , and R 6  are H; and n is greater than 1. 
 
   
   
       24 . The monomeric, oligomeric, or polymeric compound of  claim 22 , wherein said compound comprises recurring units of formula II 
     
       
         
         
             
             
         
       
     
     wherein
 R 1 , R 2 , R 3 , R 4 , R 5 , and R 6  
 are, independently of each other, and, in case of multiple occurrence, independently of one another, H; halogen; optionally substituted aryl or heteroaryl; P-Sp-; P*-Sp-; or straight chain, branched, or cyclic alkyl having up to 20 C atoms, optionally mono- or polysubstituted by F, Cl, Br, I, or CN; wherein one or more non-adjacent CH 2  groups are optionally replaced, in each case independently from one another, by —O—, —S—, —NH—, —NR 0 —, —SiR 0 R 00 —, —CO—, —COO—, —OCO—, —O—CO—O—, —S—CO—, —CO—S—, —CX 1 ═CX 2 —, or —C≡C—, with the proviso that O and/or S atoms are not linked directly to one another; 
 
 a, b, c, and d
 are, independently of each other, 0, 1, 2, or 3, wherein the sum of a and c is greater than 1 and the sum of b and d is greater than 1; 
 
 n is an integer greater than or equal to 1; 
 R 7  and R 8  
 are, independently of each other, and, in case of multiple occurrence, independently of one another, H; halogen; optionally substituted aryl or heteroaryl; P-Sp-; P*-Sp-; —Sn(R 0 ) 3 ; —B(OR′)(OR″); —CH 2 C; —CHO; —CH═CH 2 ; —SiR 0 R 00 R 000 ; or straight chain, branched, or cyclic alkyl having up to 20 C atoms, optionally mono- or polysubstituted by F, Cl, Br, I, or CN; wherein one or more non-adjacent CH 2  groups are optionally replaced, in each case independently from one another, by —O—, —S—, —NH—, —NR 0 —, —SiR 0 R 00 —, —CO—, —COO—, —OCO—, —O—CO—O—, —S—CO—, —CO—S—, —CX 1 ═CX 2 —, or —C≡C—, with the proviso that O and/or S atoms are not linked directly to one another; 
 
 R 0 , R 00 , and R 000  
 are, independently of each other, H, or aryl or alkyl having up to 12 C atoms; and 
 
 R′ and R″
 are, independently of each other, H or alkyl having up to 12 C atoms, or OR′ and OR″ together with the boron atom optionally define a cyclic group having 2 to 20 C atoms. 
 
 
   
   
       25 . The monomeric, oligomeric, or polymeric compound of  claim 22 , wherein said compound is selected from formulae I1a, I1b, I1c, I1d, I1e, or I1f; 
     
       
         
         
             
             
         
       
     
     wherein
 R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8  
 are, independently of each other, and, in case of multiple occurrence, independently of one another, H; halogen; optionally substituted aryl or heteroaryl; P-Sp-; P*-Sp-; or straight chain, branched, or cyclic alkyl having up to 20 C atoms, optionally mono- or polysubstituted by F, Cl, Br, I, or CN; wherein one or more non-adjacent C 1 H 2  groups are optionally replaced, in each case independently from one another, by —O—, —S—, —NH—, —NR 0 —, —SiR 0 R 00 —, —CO—, —COO—, —OCO—, —O—CO—O—, —S—CO—, —CO—S—, —CX 1 ═CX 2 —, or —C≡C—, with the proviso that O and/or S atoms are not linked directly to one another; 
 
 a, b, c, and d
 are, independently of each other, 0, 1, 2, or 3, wherein the sum of a and c is greater than 1 and the sum of b and d is greater than 1; and 
 
 n is an integer greater than or equal to 1. 
 
   
   
       26 . The monomeric, oligomeric, or polymeric compound of  claim 22 , wherein R 3 , R 4 , R 5 , and R 6  are H and R 1  and R 2  are different from H. 
   
   
       27 . The monomeric, oligomeric, or polymeric compound of  claim 22 , wherein R 1  and R 2  are selected from C 1  to C 20  alkyl, C 1  to C 20  alkoxy, C 1  to C 20  alkenyl, C 1  to C 20  alkynyl, C 1  to C 20  thioalkyl, C 1  to C 20  silyl, C 1  to C 20  ester, C 1  to C 20  amino, or C 1  to C 20  fluoroalkyl. 
   
   
       28 . The monomeric, oligomeric, or polymeric compound of  claim 22 , wherein R 1  and R 2  are selected from C 9  to C 20  alkyl, C 9  to C 20  alkoxy, C 6  to C 20  alkenyl, C 9  to C 20  alkynyl, C 9  to C 20  thioalkyl, C 9  to C 20  silyl, C 9  to C 20  ester, C 9  to C 20  amino, C 9  to C 20  fluoroalkyl, and optionally substituted aryl or heteroaryl. 
   
   
       29 . The monomeric, oligomeric, or polymeric compound of  claim 22 , wherein n is an integer from 2 to 5000. 
   
   
       30 . The monomeric, oligomeric, or polymeric compound of  claim 22 , wherein n is 1 and one or both of R 7  and R 8  are halogen, —Sn(R 0 ) 3 , —B(OR′)(OR″), —CH 2 Cl, —CHO, —CH═CH 2 , or —SiR 0 R 00 R 000 . 
   
   
       31 . The monomeric, oligomeric, or polymeric compound of  claim 22 , wherein n is 1 and one or both of 17 and R 8  are P-Sp- or P*-Sp-. 
   
   
       32 . The monomeric, oligomeric, or polymeric compound of  claim 22 , wherein said compound is selected from formulae I1a1, I1a2, I1c1, or I1c2: 
     
       
         
         
             
             
         
       
     
     wherein
 R 7  and R 8  
 are, independently of each other, and, in case of multiple occurrence, independently of one another, H; halogen; optionally substituted aryl or heteroaryl; P-Sp-; P*-Sp-; or straight chain, branched, or cyclic alkyl having up to 20 C atoms, optionally mono- or polysubstituted by F, Cl, Br, I, or CN; wherein one or more non-adjacent CH 2 , groups are optionally replaced, in each case independently from one another, by —O—, —S—, —NH—, —NR 0 —, —SiR 0 R 00 —, —CO—, —COO—, —OCO—, —O—CO—O—, —S—CO—, —CO—S—, —CX 1 ═CX 2 —, or —C≡C—, with the proviso that O and/or S atoms are not linked directly to one another; 
 
 R is, independently of each other, and, in case of multiple occurrence, independently of one another, halogen; optionally substituted aryl or heteroaryl; P-Sp-; P*-Sp-; or straight chain, branched, or cyclic alkyl having up to 20 C atoms, optionally mono- or polysubstituted by F, Cl, Br, I, or CN; wherein one or more non-adjacent CH 2  groups are optionally replaced, in each case independently from one another, by —O—, —S—, —NH—, —NR 0 —, —SiR 0 R 00 —, —CO—, —COO—, —OCO—, —O—CO—O—, —S—CO—, —CO—S—, —CX 1 ═CX 2 —, or —C═C—, with the proviso that O and/or S atoms are not linked directly to one another; and 
 n is an integer greater than or equal to 1. 
 
   
   
       33 . A polymerisable liquid crystal material comprising one or more monomeric, oligomeric, or polymeric compounds of  claim 22 , wherein said one or more compounds is a thienothiophene compound comprising at least one polymerisable group, and optionally comprising one or more further polymerisable compounds, wherein at least one of said thienothiophene compounds or said one or more further polymerisable compounds is mesogenic or liquid crystalline. 
   
   
       34 . An anisotropic polymer film having charge transport properties comprising the polymerisable liquid crystal material of  claim 33 , wherein said anisotropic polymer film is aligned in its liquid crystal phase into macroscopically uniform orientation and polymerised or crosslinked to fix the oriented state. 
   
   
       35 . A side chain liquid crystal polymer obtained by polymerisation of one or more monomeric, oligomeric, or polymeric compounds of  claim 22  or by grafting said compounds to a polymer backbone in a polymer analogous reaction, optionally with one or more additional mesogenic or non-mesogenic comonomers. 
   
   
       36 . An optical, electrooptical, or electronic component or device; an organic field effect transistor; an integrated circuit; a thin film transistor; a flat panel display; a radio frequency identification tag; an electroluminescent or photoluminescent device or component; an organic light emitting diode; a display backlight; a photovoltaic or sensor device; a charge injection layer; a Schottky diode; a planarising layer; an antistatic film; a conducting substrate or pattern; a battery electrode material; a photoconductor; an electrophotographic application; an electrophotographic recording; an organic memory device; an alignment layer; a cosmetic or pharmaceutical composition; a biosensor; or a biochip comprising the monomeric, oligomeric, or polymeric compound of  claim 22 . 
   
   
       37 . A semiconducting, electroluminescent, or charge transport material, component or device comprising at least one monomeric, oligomeric, or polymeric compound of  claim 22 . 
   
   
       38 . A thin film transistor or thin film transistor array for flat panel displays, a radio frequency identification tag, a field effect transistor, an electroluminescent display or backlight comprising the monomeric, oligomeric, or polymeric compound of  claim 22 . 
   
   
       39 . A security marling or device comprising a field effect transistor or radio frequency identification tag according to  claim 39 . 
   
   
       40 . The monomeric, oligomeric, or polymeric compound of  claim 22 , wherein said compound is oxidatively or reductively doped to form conducting ionic species. 
   
   
       41 . A charge injection layer, a planarising layer, an antistatic film, or a conducting substrate or pattern for electronic applications or flat panel displays comprising the monomeric, oligomeric, or polymeric compound of  claim 41 .